U.S. patent number 7,638,645 [Application Number 11/581,987] was granted by the patent office on 2009-12-29 for metal (iv) tetra-amidinate compounds and their use in vapor deposition.
This patent grant is currently assigned to President and Fellows of Harvard University. Invention is credited to Roy G. Gordon, Jean-Sebastien Lehn, Huazhi Li.
United States Patent |
7,638,645 |
Gordon , et al. |
December 29, 2009 |
**Please see images for:
( Certificate of Correction ) ** |
Metal (IV) tetra-amidinate compounds and their use in vapor
deposition
Abstract
Metal(IV) tetrakis(N,N'-dialkylamidinates) were synthesized and
characterized. Exemplary metals include hafnium, zirconium,
tantalum, niobium, tungsten, molybdenum, tin and uranium. These
compounds are volatile, highly stable thermally, and suitable for
vapor deposition of metals and their oxides, nitrides and other
compounds.
Inventors: |
Gordon; Roy G. (Cambridge,
MA), Lehn; Jean-Sebastien (Watertown, MA), Li; Huazhi
(Somerville, MA) |
Assignee: |
President and Fellows of Harvard
University (Cambridge, MA)
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Family
ID: |
38876980 |
Appl.
No.: |
11/581,987 |
Filed: |
October 17, 2006 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20080003359 A1 |
Jan 3, 2008 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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60817209 |
Jun 28, 2006 |
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Current U.S.
Class: |
556/51; 556/57;
556/45; 556/42; 556/137; 534/15; 534/11; 427/248.1 |
Current CPC
Class: |
C07C
257/14 (20130101); C23C 16/045 (20130101); C23C
16/34 (20130101); C07F 7/003 (20130101); C23C
16/45525 (20130101); C23C 16/45553 (20130101); C23C
16/405 (20130101) |
Current International
Class: |
C07F
7/00 (20060101); C07F 11/00 (20060101); C23C
16/00 (20060101); C07F 15/00 (20060101); C07F
5/00 (20060101) |
Field of
Search: |
;556/42,45,51,57,137
;534/11,15 ;427/248.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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WO-91/08322 |
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Jun 1991 |
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WO |
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WO-2004/046417 |
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Jun 2004 |
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WO |
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WO-2004/046417 |
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Jun 2004 |
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WO |
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Other References
Fix, et al., "Chemical Vapor Deposition of Titanium, Zirconium, and
Hafnium Nitride Thin Films" , American Chemical Society, vol. 3(6),
pp. 1138-1148, 1991. cited by other .
International Search Report from PCT/US2007/014768, mailed Nov. 11,
2007. cited by other.
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Primary Examiner: Gonzalez; Porfirio Nazario
Attorney, Agent or Firm: WilmerHale LLP
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit under 35 U.S.C. .sctn.119(e) of
U.S. Provisional Patent Application No. 60/817,209 filed on Jun.
28, 2006, entitled Metal(IV) Tetra-Amidinate Compounds And Their
Use In Vapor Deposition, which is incorporated herein by reference
in its entirety.
Claims
What is claimed is:
1. A compound having the structural formula ##STR00005## in which M
is a metal in the +4 oxidation state and each of R.sup.1 through
R.sup.12 are independently selected from the group consisting of
hydrogen, hydrocarbon groups, substituted hydrocarbon groups, and
other groups comprising non-metallic atoms.
2. The compound of claim 1, wherein the hydrocarbon group is
selected from the group consisting of alkyl, cycloalkyl, alkenyl,
cycloalkenyl, alkynyl and cycloalkynyl groups and the substituted
hydrocarbon group consisting of fluoride derivatives of
hydrocarbons.
3. The compound of claim 1, wherein the group comprising
non-metallic atoms are selected from the group consisting of
alkylsilyl and alkyl amino groups.
4. The compound of claim 1, wherein metal M is selected from the
group consisting of zirconium, hafnium, tin, tantalum, niobium,
tungsten, molybdenum, uranium, rhenium, platinum, osmium, iridium,
ruthenium, palladium, titanium, rhodium, vanadium, cerium and
lead.
5. The compound of claim 1, in which the metal M is selected from
the group consisting of hafnium, zirconium, tantalum, niobium,
tungsten, molybdenum, tin, tellurium and uranium.
6. The compound of claim 1, in which the metal M is zirconium.
7. The compound of claim 1, in which the metal M is hafnium.
8. The compound of claim 1, wherein at least one of R.sup.1 through
R.sup.12 is a lower alkyl having 5 or less carbons.
9. The compound of claim 1, wherein R.sup.1 through R.sup.12 is
selected from the group consisting of lower alkyls having 5 or less
carbons and hydrogen.
10. The compound of claim 1, wherein R.sup.1, R.sup.3, R.sup.4,
R.sup.6, R.sup.7, R.sup.9, R.sup.10 and R.sup.12 are alkyl groups
that are un-branched at the .alpha.-position.
11. A process for forming a thin film comprising a metal,
comprising: exposing a heated surface to a vapor of one or more
volatile compounds of claim 1.
12. The process of claim 11, wherein the hydrocarbon group is
selected from the group consisting of alkyl, cycloalkyl, alkenyl,
cycloalkenyl, alkynyl and cycloalkynyl groups and fluoride
derivatives thereof.
13. The process of claim 11, wherein the group comprising
non-metallic atoms are selected from the group consisting of
alkylsilyl and alkyl amino groups.
14. The process of claim 11, wherein the metal M is selected from
the group consisting of zirconium, hafnium, tin, tantalum, niobium,
tungsten, molybdenum, uranium, rhenium, platinum, osmium, iridium,
ruthenium, palladium, titanium, rhodium, vanadium, cerium,
tellurium and lead.
15. The process of claim 11, wherein the metal M is selected from
the group consisting of hafnium, zirconium, tantalum, niobium,
tungsten, molybdenum, tin, tellurium and uranium.
16. The process of claim 11, wherein the metal M is zirconium.
17. The process of claim 11, wherein the metal M is hafnium.
18. The process of claim 11, wherein at least one of R.sup.1
through R.sup.12 is a lower alkyl having 5 or less carbons.
19. The process of claim 11, wherein R.sup.1 through R.sup.12 is
selected from the group consisting of lower alkyls having 5 or less
carbons and hydrogen.
20. The process of claim 11, in which the substrate is also exposed
to a source of oxygen, and the thin film comprises a metal
oxide.
21. The process of claim 20, in which the source of oxygen
comprises water vapor.
22. The process of claim 20, in which the source of oxygen
comprises dioxygen.
23. The process of claim 20, in which the source of oxygen
comprises ozone.
24. The process of claim 11, in which the substrate is also exposed
to a source of nitrogen, and the thin film comprises a metal
nitride.
25. The process of claim 24, in which the source of nitrogen
comprises ammonia.
26. The process of claim 11, wherein the film is deposited in a CVD
process.
27. The process of claim 11, wherein the film is deposited in an
ALD process.
28. The process of claim 11, wherein the vapor is obtained by
vaporizing a solid form of the compound.
29. The process of claim 11, wherein the vapor is obtained by
vaporizing a liquid form of the compound.
30. The process of claim 11, wherein the vapor is obtained by
vaporizing the compound at a temperature in the range of 100 to
250.degree. C.
31. The process of claim 11, wherein the surface is at a
temperature in the range of about 200 to 500.degree. C.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel compounds containing metals in the
+4 oxidation state bonded to four amidinate ligands. This invention
also relates to the use of these compounds as precursors for vapor
deposition of metal-containing layers.
2. Description of the Related Art
Electrically insulating materials with high dielectric constants
("high-k dielectrics") are now being used in the manufacture of
computer memories (dynamic random access memories, or DRAMs).
Aluminum oxide and tantalum oxide are currently in commercial use
in DRAMs, and oxides, nitrides and silicates of hafnium and
zirconium are being tested as alternatives for future use. These
high-k materials may also be used as insulators in future
transistors in microelectronic devices.
Electrically conductive nitrides of metals such as tantalum,
tungsten, hafnium, zirconium, titanium, niobium and molybdenum have
a variety of applications and potential applications, such as
barriers against the diffusion of copper, and as electrodes for
capacitors and transistors in microelectronic devices. These
refractory metals also find use as adhesion-promoting layers for
copper, and as electrodes or electrical interconnections.
Vapor deposition is a preferred method for making these materials.
Vapor deposition is a generic term that comprises chemical vapor
deposition (CVD) and atomic layer deposition (ALD). In a CVD
process, one or more vapors are delivered to a surface on which
solid material is deposited; the chemical reactions that convert
the vapor to a solid are initiated by means such as heat, light or
electrical excitation (plasma activation). In an ALD process, two
or more vapors are delivered alternately to the surface on which
reactions take place to deposit a solid product. ALD is capable of
depositing these materials inside the very narrow structures in
modern DRAMs. CVD generally provides higher deposition rates than
ALD, but with less uniform deposition inside very narrow holes.
Successful precursors for vapor deposition must be volatile,
thermally stable, and highly reactive. Identifying compounds that
meet all of these challenging requirements is difficult. Fully
satisfactory precursors for metals such as hafnium, zirconium,
tantalum, niobium, tungsten, molybdenum, tin, tellurium and uranium
are not known. Halides, such as ZrCl.sub.4, HfCl.sub.4, and
TaCl.sub.5, have difficulty nucleating on some substrate surfaces,
and the byproduct hydrochloric acid prevents fully conformal
deposition inside narrow holes. Alkoxides and dialkylamides have
less than optimal thermal stabilities. Organometallic compounds may
lack suitable reactivity, leaving carbon as an impurity in the
films. Thus there is a need for more volatile, thermally stable,
and highly reactive sources for these metals.
SUMMARY OF THE INVENTION
One aspect of the invention includes novel compounds containing
metals in the +4 oxidation state bonded to four amidinate ligands.
In preferred embodiments, these ligands comprise
N,N'-dialkylamidinate ligands. Preferred metals include hafnium,
zirconium, tantalum, niobium, tungsten, molybdenum, tin, tellurium
and uranium.
In one or more embodiments, the compound has the structural
formula
##STR00001## in which M is a metal in the +4 oxidation state and
each of R.sup.1 through R.sup.12 are independently selected from
the group consisting of hydrogen, hydrocarbon groups, substituted
hydrocarbon groups, and other groups of non-metallic atoms.
In one or more embodiments, the hydrocarbon group is selected from
the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl,
alkynyl and cycloalkynyl groups and the substituted hydrocarbon
group consisting of fluoride derivatives of hydrocarbons, or the
group comprising non-metallic atoms are selected from the group
consisting of alkylsilyl and alkyl amino groups.
In one or more embodiments, the metal M is selected from the group
consisting of zirconium, hafnium, tin, tantalum, niobium, tungsten,
molybdenum, uranium, rhenium, platinum, osmium, iridium, ruthenium,
palladium, titanium, rhodium, vanadium, cerium and lead, or the
metal M is selected from the group consisting of hafnium,
zirconium, tantalum, niobium, tungsten, molybdenum, tin, tellurium
and uranium.
In one or more embodiments, at least one of R.sup.1 through
R.sup.12 is a lower alkyl having 5 or less carbons.
In one or more embodiments, R.sup.1 through R.sup.12 is selected
from the group consisting of lower alkyls having 5 or less carbons
and hydrogen.
In one or more embodiments, R.sup.1, R.sup.3, R.sup.4, R.sup.6,
R.sup.7, R.sup.9, R.sup.10 and R.sup.12 are alkyl groups that are
un-branched at the .alpha.-position.
Another aspect of the present invention includes a process for
depositing films comprising metals using the novel compounds
according to one or more embodiments of the invention. The process
includes exposing a heated surface to the vapor of one or more
volatile metal tetra-amidinate compounds. Exemplary deposition
methods include Chemical Vapor Deposition (CVD) and Atomic Layer
Deposition (ALD).
In one or more embodiments, the process includes exposing the
substrate to a source of oxygen, and the thin film comprises a
metal oxide.
In one or more embodiments, the source of oxygen comprises water
vapor, or dioxygen, or ozone.
In one or more embodiments, the process includes exposing the
substrate to a source of nitrogen, and the thin film comprises a
metal nitride.
In one or more embodiments, the source of nitrogen comprises
ammonia.
In one or more embodiments, the vapor is obtained by vaporizing a
solid metal tetra-amidinate compound, or by vaporizing a liquid
metal tetra-amidinate compound.
In one or more embodiments, the vapor is obtained by vaporizing a
metal tetra-amidinate at a temperature in the range of 100 to
250.degree. C.
In one or more embodiments, the surface is at a temperature in the
range of about 200 to 500.degree. C.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and various other aspects, features, and advantages
of the present invention, as well as the invention itself, may be
more fully appreciated with reference to the following detailed
description of the invention when considered in connection with the
following drawings. The drawings are presented for the purpose of
illustration only and are not intended to be limiting of the
invention, in which:
FIG. 1 is a schematic cross-sectional drawing of an ALD apparatus
that can be used in some embodiments of the invention;
FIG. 2 is a drawing of the molecular structure of
tetrakis(N,N'-di-iso-butylacetamidinato) zirconium(IV); and
FIG. 3 is a drawing of the molecular structure of
tetrakis(N,N'-dimethylpropionamidinato) hafnium(IV).
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides thermally stable, volatile metal
compounds that are suitable for use in vapor deposition processes,
including chemical vapor deposition and atomic layer
deposition.
Preferred compounds include volatile metal(IV)
tetrakis(N,N'-dialkylamidinates) complexes. Typically, these
compounds are described by a monomeric formula 1,
##STR00002## in which M is a metal in the +4 oxidation state and
R.sup.1 through R.sup.12, e.g., R.sup.n, where n=1-12, may be
independently chosen from hydrogen, hydrocarbon groups such as
alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl and cycloalkynyl
groups and fluoride derivatives thereof, or other groups comprising
non-metallic atoms such as alkylsilyl and alkyl amino groups.
Reference to R.sup.n applies equally to each of R.sup.1 through
R.sup.12, unless otherwise specified.
In one or more embodiments, R.sup.n are lower alkyl groups
containing 5 or less carbons. In one or more embodiments, R.sup.n
are a mixture of hydrogen and lower alkyl groups. In preferred
embodiments R.sup.n are chosen from the group comprising methyl,
ethyl and n-propyl. These small alkyl groups are preferred because
they are small enough to fit into the structure 1 with very stable
chelate binding. In one or more embodiments, one or more of
R.sup.1, R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.9, R.sup.10or
R.sup.12 are hydrocarbon groups lacking a branched .alpha.-carbon.
As used herein, an .alpha.-carbon is a carbon bound directly to one
nitrogen of an amidinate ligand. Alkyl groups that branch at the
.alpha.-carbon, such as isopropyl, sec-butyl or tert-butyl, are
less preferred because they are likely to cause too much crowding
to fit into structure 1. Thus the branched alkyl groups will
generally provide less stable metal amidinates. Nonetheless,
branched groups are contemplated according to one or more
embodiments, in particular, where a larger metal center is used or
the branching occurs beyond the .alpha.-carbon.
Exemplary tetravalent metals that may be used in one or more
embodiments of the invention include zirconium, hafnium, tin,
tantalum, niobium, tungsten, molybdenum, uranium, rhenium,
platinum, osmium, iridium, ruthenium, palladium, titanium, rhodium,
vanadium, cerium, tellurium and lead. Tetravalent metal ions having
relatively larger ionic radii form tetra-amidinate complexes that
are particularly stable; those metals include zirconium, hafnium,
tin, tantalum, niobium, tungsten, molybdenum, tellurium and
uranium. Tetravalent metal ions having relatively smaller ionic
radii that form tetra-amidinate include rhenium, platinum, osmium,
iridium, ruthenium, palladium, titanium, rhodium and vanadium.
In one or more embodiments, the amidinate ligand is symmetric,
e.g., the N-bound R groups such as R.sup.1 and R.sup.3 or R.sup.4
and R.sup.6, etc., are the same in formula 1. In one or more
embodiments, the amidinate ligand is asymmetric, e.g., R.sup.1 and
R.sup.3 are different in formula 1. In either embodiment, the
carbon-bound R group, e.g., R.sup.2 in formula 1, can be the same
or different.
In one or more embodiments, metal tetrakis(N,N'-dialkylamidinate)
compounds are prepared using N,N'-dialkylamidines. Symmetric
amidines may be formed by condensation of amines with nitriles
catalyzed by lanthanum trifluoromethanesulfonate (also known as
lanthanum triflate), La(CF.sub.3SO.sub.3).sub.3:
##STR00003##
Amines in which R.sup.1 is an alkyl group that is not branched at
the .alpha.-position, such as n-propyl, n-butyl or isobutyl, react
within a few hours to a few days at reflux temperature. Amines in
which R.sup.1 is a methyl or ethyl group are so volatile that they
must be confined within a pressure vessel during the reaction.
During the course of the reaction the byproduct ammonia may be
released from the pressure vessel by a back-pressure regulator.
Complete reaction takes a few days at room temperature, or shorter
periods at higher temperatures and pressures. A less expensive
catalyst for this reaction can be made from mixed triflates of the
naturally-occurring mixture of lanthanum metals ("misch
metal").
Unsymmetrical amidines can be prepared according to the following
reactions:
##STR00004##
Metal amidinates can be prepared by exchange reactions in which a
metal dialkylamide is reacted with an amidine. Alternately, the
amidine can be converted to its alkali salt by reaction with
butyllithium or with sodium amide or with potassium hydride. The
alkali amidinate can then undergo a salt metathesis reaction with a
metal chloride to form the metal amidinate. A more commonly-used
method to form lithium amidinates is to react a carbodiimide with a
lithium alkyl. This conventional synthetic route is more effective
when the R.sup.1 and R.sup.3 alkyl groups are branched at the
.alpha.-position, because the corresponding carbodiimides are more
stable.
The metal tetra-amidinate compounds may be used to form
metal-containing films in a vapor deposition process. Vapors of the
compounds according to one or more embodiments may be used to
deposit materials such as metals, metal oxides, metal nitrides,
metal oxynitrides, metal sulfides and the like. These vapor
deposition processes include CVD and ALD. In CVD, a vapor of the
metal tetra-amidinate is supplied to the surface, optionally along
with a co-reactant gas or vapor. In ALD, a vapor of the metal
tetra-amidinate and a co-reactant are supplied to the surface in
alternating time periods. CVD processing is described, for example,
in U.S. Pat. No. 5,139,999, which is hereby incorporated by
reference, and in the "Handbook of Chemical Vapor Deposition:
Principles, Technology and Applications" by Hugh O. Pierson
(2.sup.nd edition, Noyes Publications, 1999). ALD processing is
described in U.S. Pat. No. 6,969,539, which is hereby incorporated
by reference, and in the article "Atomic Layer Deposition" by M.
Ritala and M. Leskela, vol. 1, p. 103 of the Handbook of Thin Film
Materials (Ed. H. Nalwa, Academic Press, 2002). Oxides may be
formed using co-reactants such as water vapor, dioxygen, ozone,
hydrogen peroxide and alcohols or a plasma formed from an
oxygen-containing gas or vapor. Nitrides may be formed using
co-reactants such as ammonia, a hydrazine or a plasma formed from a
nitrogen-containing gas or vapor. Sulfides may be formed using
co-reactants such as hydrogen sulfide or a plasma formed from a
sulfur-containing gas or vapor.
An apparatus for carrying out ALD is shown schematically in
cross-section in FIG. 1. During operation of the ALD process,
carrier gas, such as nitrogen, flows continuously from sources 91
and 92 through the deposition chamber 110 into pipe 150 to a trap
and vacuum pump. A tetra-amidinate precursor 21 is held in vessel
11 that is heated in oven 41 to a temperature sufficient to form
its vapor 31. Vapor 31 of the tetravalent amidinate precursor flows
into evacuated chamber 61 in oven 81 when valve 51 is opened. Valve
51 is then closed and valve 71 opened to allow an aliquot of
precursor vapor to flow over the substrate 130 inside heated
furnace 120. Valve 71 is then closed and time is allowed for excess
unreacted precursor to be purged from chamber 110 along with
volatile reaction byproducts. The second reagent 22, such as water
or ammonia, is placed in vessel 12, usually kept at room
temperature. Vapor 32 of the second reagent is allowed to flow into
vapor space 62 by opening valve 52, which is then closed. Valve 72
is opened to allow an aliquot of the second reagent to flow into
the deposition chamber 110. Valve 72 is then closed and time is
allowed for unreacted excess of the second reagent to be purged
from the deposition chamber 110 along with volatile reaction
byproducts. This cycle of operations is then repeated to build up
the desired thickness of coating on substrate 130.
An apparatus for carrying out CVD includes many similar features.
The apparatus may include a vessel housing a tetra-amidinate
precursor that is heated to a temperature to form its vapor. The
tetra-amidinate precursor vapor flows from the vessel and into a
heated furnace housing the substrate. Additional co-reactant vapors
may be introduced into the heated furnace with the tetra-amidinate
precursor, or the co-reactant vapors may be premixed with the
tetra-amidinate vapor prior to their exposure to the heated
substrate. An exhaust system removes byproducts and unreacted
reactants from the furnace.
The tetra-amidinate precursor may be used as a neat liquid, in
solution in the appropriate solvent, or as a solid. Suitable
deposition conditions, such as temperatures for vaporization and
deposition, pressures, flow rates, and co-reactants may be readily
determined by one of skill in the art. Exemplary ALD and CVD
conditions include substrate temperatures of 200 to 500.degree. C.,
and more preferably 300 to 400.degree. C., vapor pressures in the
range of 0.1 to 10 Torr, and more preferably 1 to 5 Torr,
vaporization temperatures of about 100 to 250.degree. C., and more
preferably 150 to 200.degree. C., ALD doses of 1 to 100 nmol
cm.sup.-2 of deposited surface, and more preferably 2 to 20 nmol
cm.sup.-2, and ALD exposures of 0.01 Torr-sec to 10 Torr-sec, and
more preferably 0.1 to 1 Torr-sec. The ALD exposures needed to
cover features with high aspect ratios increase approximately as
the square of the aspect ratio.
EXAMPLES
Example 1
Synthesis of N,N'-di-iso-butylacetamidine
A solution of iso-butylamine (7.3 g, 0.1 mol), acetonitrile (4.1 g,
0.1 mol) and lanthanum triflate, La(CF.sub.3SO.sub.3).sub.3, (1.2
g, 0.002 mol) was refluxed for 30 hr under nitrogen atmosphere. The
unreacted starting material and byproduct
2,4,6-trimethyl-1,3,5-triazine were removed by fractional
distillation at 40.degree. C. at around 0.2 Torr. Then the
colorless N,N'-di-iso-butylacetamidine was distilled at 95.degree.
C. and 0.06 torr. Further purification was done by a second
distillation. Yield: 6.4 g (75% based on iso-butylamine). .sup.1H
NMR (benzene-d.sub.6+a small amount of CD.sub.3OD, ppm): 3.1 (d, 4,
NCH.sub.2), 1.9 (m, 2, CH(CH.sub.3).sub.2), 1.7 (s, 3, CCH.sub.3),
1.0 (d, 12, CH(CH.sub.3).sub.2).
Example 2
Synthesis of tetrakis(N,N'-di-iso-butylacetamidinato)zirconium(IV),
Zr(.sup.iBu-AMD).sub.4
0.8 g (3 mmol) of tetrakis(dimethylamido)zirconium(IV),
Zr(NMe.sub.2).sub.4, was dissolved in 10 ml of toluene and then
cooled to -30.degree. C. for 30 minutes. To this solution was added
2.3 g (13.5 mmol) N,N'-di-iso-butylacetamidine, .sup.iBu-AMD, and
the mixture was heated at 90.degree. C. overnight (ligand exchange
reaction). After cooling to -30.degree. C., a colorless crystalline
material precipitated and was filtered out. Yield: 1.85 g (80%).
.sup.1H NMR (benzene-d.sub.6, ppm): 3.10 (d, 16, J=6.9 Hz,
NCH.sub.2), 1.89 (m, 8, CH(CH.sub.3).sub.2), 1.71 (s, 12,
CCH.sub.3), 1.00 (d, 48, J=6.6 Hz, d, CH(CH.sub.3).sub.2). .sup.13C
NMR (benzene-d.sub.6, ppm): 174 (CCH.sub.3), 55.76 (NCH.sub.2),
31.74 (CH(CH.sub.3).sub.2), 21.134 (CH(CH.sub.3).sub.2, 12.10
(CCH.sub.3). Anal. Calcd. for C.sub.40H.sub.84N.sub.8Zr: C, 62.53;
H, 11.02; N, 14.58. Found: C, 62.76; H, 11.25; N, 14.50.
X-ray crystallography was used to determine the molecular structure
of tetrakis(N,N'-di-iso-butylacetamidinato)zirconium(IV) shown in
FIG. 2, where the atoms are represented by 50% thermal ellipsoids
and hydrogen atoms are omitted for clarity. Each molecule contains
one zirconium atom surrounded by 8 nitrogen atoms from the four
amidinate ligands.
The temperature at which half of the product evaporated during
thermogravimetric analysis (TG), T.sub.1/2, is 240.degree. C.,
measured in flowing nitrogen gas at atmospheric pressure. This TG
experiment also demonstrated that the compound has a high thermal
stability and completely vaporizes with negligible residue.
Example 3
Synthesis of tetrakis(N,N'-di-iso-butylacetamidinato)hafnium(IV),
Hf(.sup.iBu-AMD).sub.4
This compound was prepared in a way similar to that described in
Example 2 for Zr(.sup.iBu-AMD).sub.4, starting from 3 mmol of
tetrakis(dimethylamido)hafnium(IV), Hf(NMe.sub.2).sub.4. The
product was isolated as a white powder. Yield: 2.17 g (85%).
.sup.1H NMR (benzene-d.sub.6, ppm): 3.15 (d, 16, J=7.2 Hz,
NCH.sub.2), 1.87 (m, 8, CH(CH.sub.3).sub.2), 1.70 (s, 12,
CCH.sub.3), 0.99 (d, 48, J=6.8 Hz, CH(CH.sub.3).sub.2). Anal.
Calcd. for C.sub.40H.sub.84HfN.sub.8: C, 56.15; H, 9.90; N, 13.10.
Found: 55.85; H, 9.77; N, 13.30.
The TG properties of this hafnium complex are similar to those of
the zirconium complex described in Example 2.
Example 4
Synthesis of N,N'-dimethylacetamidine and its Lithium Salt
Anhydrous lanthanum triflate (3.00 g, 5.12 mmol) was placed into a
pressure vessel. Dry acetonitrile (23.3 g, 0.568 mol) was condensed
into the cold vessel. The vessel was cooled with liquid nitrogen
and dry methylamine (53.1 g, 1.71 mol) was added. The vessel was
sealed and allowed to warm to room temperature. Byproduct ammonia
gas was released daily. Reaction was mostly complete after 3 days.
Then the colorless N,N'-dimethylacetamidine was isolated by
removing the byproduct N-methylacetamidine by sublimation at
20.degree. C. and 0.04 torr. .sup.1H NMR (benzene-d.sub.6, ppm):
2.60 (s, 6, NCH.sub.3), 1.40 (s, 3, CCH.sub.3).
The lithium salt of N,N'-dimethylacetamidine was prepared by
dissolving one volume of N,N'-dimethylacetamidine in 5 volumes of
dry ether and cooling the solution to -78.degree. C. An equal molar
amount of butyllithium dissolved in hexanes was added slowly while
stirring. The reaction mixture was allowed to warm to room
temperature. The ether and pentane were removed under reduced
pressure. Then the white solid residue was dissolved in dry
dioxane. The resulting solution of
N,N'-dimethylacetamidinato-lithium in dioxane was used in some of
the following examples.
Example 5
Synthesis of tetrakis(N,N'-dimethylacetamidinato)zirconium(IV)
This compound was prepared by ligand exchange in a way similar to
that described in Example 2 for Zr(.sup.iBu-AMD).sub.4, using
N,N'-dimethylacetamidine in place of N,N'-di-iso-butylacetamidine.
Alternatively, ZrCl.sub.4 was reacted with the lithium salt of
N,N'-dimethylacetamidine dissolved in dioxane (salt metathesis
reaction). This reaction mixture was heated to reflux for 8 hours.
After evaporation of the dioxane, the solid residue was extracted
with pentane. After decantation of the suspension to remove the
precipitated lithium chloride, the pentane was evaporated under
reduced pressure to yield the crude product, which was then
purified by sublimation at 60.degree. C. and a pressure of 40 mbar.
It can also be sublimed at atmospheric pressure at 160.degree. C.
The yield was 24% after sublimation, when the synthesis was done on
a small scale. .sup.1H NMR (benzene-d.sub.6, ppm); 3.03 (s, 24,
NCH.sub.3), 1.57 (s, 12, CCH.sub.3). .sup.13C NMR (benzene-d.sub.6,
ppm): 175.99 (s, CCH.sub.3), 34.55 (s, NCH.sub.3), 9.84 (s,
CCH.sub.3). Anal. Calcd. for C.sub.16H.sub.36N.sub.8Zr: C, 44.51;
H, 8.40; N, 25.95. Found: C, 45.31; H, 7.92; N, 25.60; or, in a
second analysis, C, 43.30; H, 8.76; N, 24.87. This product is more
volatile than
tetrakis(N,N'-di-iso-butylacetamidinato)zirconium(IV), the product
of Example 2 because its T.sub.1/2 value from the TG curve is
216.degree. C. with 0.6% residue. Its melting point is about
168.degree. C.
Example 6
Synthesis of tetrakis(N,N'-dimethylacetamidinato)hafnium(IV)
This compound was prepared from HfCl.sub.4 by the salt metathesis
reaction described in Example 5. .sup.1H NMR (benzene-d.sub.6,
ppm); 3.07 (s, 24, NCH.sub.3), 1.55 (s, 12, CCH.sub.3). .sup.13C
NMR (benzene-d.sub.6, ppm); 175.69 (s, CCH.sub.3), 34.31 (s,
NCH.sub.3), 10.09 (s, CCH.sub.3). Anal. Calcd. for
C.sub.16H.sub.36HfN.sub.8: C, 37.03; H, 6.99; N, 21.59. Found:
37.00; H, 6.89; N, 21.34. This product is more volatile than
tetrakis(N,N'-di-iso-butylacetamidinato)hafnium(IV), the product of
Example 3 because its T.sub.1/2 value from the TG curve is
221.degree. C. Its residue after evaporation is negligible, less
than 1%, and its melting point is about 171.degree. C.
Example 7
Synthesis of
tetrakis(N,N'-dimethylpropionamidinato)zirconium(IV)
A dioxane solution of lithium N,N'-dimethylpropionamidinate was
prepared by the method described in Example 4, using propionitrile
in place of acetonitrile. This solution was then used with
ZrCl.sub.4 in the salt metathesis method described in Example 5 to
prepare tetrakis(N,N'-dimethylpropionamidinato)zirconium(IV). This
compound may also be prepared by a ligand exchange reaction similar
to the one described in Example 2. .sup.1H NMR (benzene-d.sub.6,
ppm); 3.07 (s, 24, NCH.sub.3), 2.10 (q, 8, J=7.6 Hz,
CH.sub.2CH.sub.3), 0.96 (t, 12, J=7.6 Hz, CH.sub.2CH.sub.3).
.sup.13C NMR (benzene-d.sub.6, ppm); 180.12 (s, CCH.sub.2CH.sub.3),
33.92 (s, NCH.sub.3), 17.31 (s, CCH.sub.2CH.sub.3), 10.41 (s,
CCH.sub.2CH.sub.3). Anal. Calcd. for C.sub.20H.sub.44N.sub.8Zr: C,
49.24; H, 9.09; N, 22.97. Found: 49.42; H, 9.04; N, 22.43. Its
melting point is 109.degree. C., which is low enough so that it is
a liquid at a temperature high enough to vaporize it in a bubbler.
Its T.sub.1/2 value from the TG curve is 245.degree. C. with a
negligible residue of 0.6%.
Example 8
Synthesis of tetrakis(N,N'-dimethylpropionamidinato)hafnium(IV)
This compound was prepared from HfCl.sub.4 by the salt metathesis
reaction described in Example 7. It may also be prepared by a
ligand exchange reaction similar to the one described in Example 1.
.sup.1H NMR (benzene-d.sub.6, ppm): 3.10 (s, 24, NCH.sub.3), 2.08
(q, 8, J=7.6 Hz, CH.sub.2CH.sub.3), 0.95 (t, 12, J=7.6 Hz,
CH.sub.2CH.sub.3). .sup.13C NMR (benzene-d.sub.6, ppm): 179.75 (s,
CCH.sub.2CH.sub.3), 33.71 (s, NCH.sub.3), 17.51 (s,
CCH.sub.2CH.sub.3), 10.40 (s, CCH.sub.2CH.sub.3). Anal. Calcd. for
C.sub.20H.sub.44HfN.sub.8: C, 41.77; H, 7.71; N, 19.48. Found:
42.32; H, 8.11; N, 19.18. Its melting point is 114.degree. C.,
which is low enough so that it is a liquid at a temperature high
enough to vaporize it in a bubbler. Its T.sub.1/2 value from the TG
curve is 252.degree. C., with a negligible non-volatile residue.
X-ray crystallography was used to determine the molecular structure
of tetrakis(N,N'-dimethylpropionamidinato)hafnium(IV) shown in FIG.
3, where the atoms are represented by 50% thermal ellipsoids and
hydrogen atoms are omitted for clarity. Each molecule contains one
hafnium atom surrounded by 8 nitrogen atoms from the four amidinate
ligands.
Example 9
Synthesis of tetrakis(N,N'-dimethylbutyramidinato)zirconium(IV)
A dioxane solution of lithium N,N'-dimethylbutyramidinate was
prepared by the method described in Example 4, using butyronitrile
in place of acetonitrile. This solution was then used with
ZrCl.sub.4 in the salt metathesis method described in Example 5 to
prepare tetrakis(N,N'-dimethylbutyramidinato)zirconium(IV). This
compound may also be prepared by a ligand exchange reaction similar
to the one described in Example 1. The compound is a liquid at room
temperature, so it was purified by distillation instead of
sublimation. .sup.1H NMR (benzene-d.sub.6, ppm); 3.11 (s, 24,
NCH.sub.3), 2.15 (t, 8, J=8.0 Hz, CCH.sub.2CH.sub.2CH.sub.3), 1.49
(m, 8, CCH.sub.2CH.sub.2CH.sub.3), 0.90 (t, 12, J=6.8 Hz,
CCH.sub.2CH.sub.2CH.sub.3). .sup.13C NMR (benzene-d.sub.6, ppm);
179.27 (s, CCH.sub.2CH.sub.2CH.sub.3), 34.28 (s, NCH.sub.3), 26.14
(s, CCH.sub.2CH.sub.2CH.sub.3), 19.82 (s,
CCH.sub.2CH.sub.2CH.sub.3), 14.47 (s,
CCH.sub.2CH.sub.2CH.sub.3).
Anal. Calcd. for C.sub.24H.sub.52N.sub.8Zr: C, 52.99; H, 9.63; N,
20.60. Found: 53.63; H, 9.87; N, 20.89. Its T.sub.1/2 value is
246.degree. C. and it evaporates leaving a negligible residue.
Example 10
Synthesis of tetrakis(N,N'-dimethylbutyramidinato)hafnium(IV)
This compound was prepared from HfCl.sub.4 by the salt metathesis
reaction described in Example 9. It may also be prepared by a
ligand exchange reaction similar to the one described in Example 1.
The compound is a liquid at room temperature, so it was purified by
distillation instead of sublimation. .sup.1H NMR (benzene-d.sub.6,
ppm): 3.15 (s, 24, NCH.sub.3), 2.13 (t, 8, J=8.0 Hz,
CCH.sub.2CH.sub.2CH.sub.3), 1.49 (m, 8, CCH.sub.2CH.sub.2CH.sub.3),
0.89 (t, 12, J=6.8 Hz, CCH.sub.2CH.sub.2CH.sub.3). .sup.13C NMR
(benzene-d.sub.6, ppm): 178.87 (s, CCH.sub.2CH.sub.2CH.sub.3),
34.08 (s, NCH.sub.3), 26.29 (s, CCH.sub.2CH.sub.2CH.sub.3), 19.82
(s, CCH.sub.2CH.sub.2CH.sub.3), 14.41 (s,
CCH.sub.2CH.sub.2CH.sub.3). Anal. Calcd. for
C.sub.24H.sub.52HfN.sub.8: C, 45.67; H, 8.30; N, 17.75. Found:
45.31; H, 8.81; N, 17.61. Its T.sub.1/2 value is 252.degree. C. and
it evaporates leaving a negligible residue.
Example 11
Synthesis of tetrakis(N,N'-diethylacetamidinato)zirconium(IV)
A dioxane solution of lithium N,N'-diethylacetamidinate was
prepared by the method described in Example 4, using ethylamine in
place of methylamine. This solution was then used with ZrCl.sub.4
in the salt metathesis method described in Example 5 to prepare
tetrakis(N,N'-diethylacetamidinato)zirconium(IV). It may also be
prepared by a ligand exchange reaction similar to the one described
in Example 1. .sup.1H NMR (benzene-d.sub.6, ppm)-3.32 (q, 16, J=7.2
Hz, NCH.sub.2CH.sub.3), 1.63 (s, 12, CCH.sub.3), 1.10 (t, 24, J=7.2
Hz, NCH.sub.2CH.sub.3). .sup.13C NMR (benzene-d.sub.6, ppm); 173.59
(s, CCH.sub.3), 41.38 (s, NCH.sub.2CH.sub.3), 18.00 (s,
NCH.sub.2CH.sub.3), 10.20 (s, CCH.sub.3). Anal. Calcd. for
C.sub.24H.sub.52N.sub.8Zr: C, 52.99; H, 9.63; N, 20.60. Found:
52.86; H, 9.40; N, 20.99. Its T.sub.1/2 value is 242.degree. C. and
it evaporates leaving a negligible residue.
Example 12
Synthesis of tetrakis(N,N'-diethylacetamidinato)hafnium(IV)
This compound was prepared from HfCl.sub.4 by the salt metathesis
method described in Example 11. It may also be prepared by a ligand
exchange reaction similar to the one described in Example 1.
.sup.1H NMR (benzene-d.sub.6, ppm): 3.32 (q, 16, J=7.2 Hz,
NCH.sub.2CH.sub.3), 1.63 (s, 12, CCH.sub.3), 1.10 (t, 24, J=7.2 Hz,
NCH.sub.2CH.sub.3). .sup.13C NMR (benzene-d.sub.6, ppm): 173.07 (s,
CCH.sub.3), 41.08 (s, NCH.sub.2CH.sub.3), 18.00 (s,
NCH.sub.2CH.sub.3), 10.59 (s, CCH.sub.3). Anal. Calcd. for
C.sub.24H.sub.52N.sub.8Hf: C, 45.67; H, 8.30; N, 17.75. Found:
46.17; H, 7.93; N, 17.27. Its T.sub.1/2 value is 264.degree. C. and
it evaporates leaving a negligible residue.
Example 13
Synthesis of tetrakis(N,N'-diethylacetamidinato)tantalum(IV)
This compound was prepared in two steps from tantalum
pentachloride. The first step involved the addition under nitrogen
at -78.degree. C. of an ether solution of tantalum pentachloride
(0.95 mmol, 331 mg in 20 mL ether) to a solution of lithium
N,N'-diethylacetamidinate (2 mmol in 20 mL ether, prepared in situ
from the amidine and a hexanes solution (2.6 M) of n-butyl
lithium). The intermediate, tentatively described as
trischloro-bis(N,N'-diethylacetamidinato)tantalum(V) was partially
soluble in ether, giving an orange solution. Some dioxane was added
to help dissolve the intermediate, and two more equivalents of
lithium N,N'-diethylacetamidinate (2 mmol in 20 mL ether, prepared
in situ from the amidine and a hexanes solution (2.6 M) of n-butyl
lithium) were added at room temperature. One equivalent of sodium
amalgam was also added (22.8 mg, in a mercury amalgam having 0.645%
sodium by weight, 3.53 g). The solution was stirred overnight at
room temperature. The solution turned dark purple within 12 hours.
The ether was stripped under vacuum, and pentane (20 mL) was added.
The purple solution was decanted and separated from the mercury and
the insoluble materials. It was dried under vacuum and yielded the
product, a purple solid, which can tentatively be described as
tetrakis(N,N'-diethylacetamidinato)tantalum(IV). The product could
be sublimed under vacuum, and the sublimed fraction could also be
sublimed again without decomposition at 150.degree. C. at a
pressure of 0.01 mmHg. Although the product contained impurities,
its color and the fact it could be sublimed under vacuum with no
decomposition indicate it is likely to be a volatile tantalum(IV)
amidinate.
Example 14
Synthesis of other metal(IV) tetra-amidinates
Compounds containing other metal centers can be prepared in ways
similar to those described in Example 3, by using a suitable metal
source in place of ZrCl.sub.4. For example,
tetrakis(N,N'-dimethylacetamidinato) tungsten(IV) is prepared using
tungsten(IV) chloride, WCl.sub.4;
tetrakis(N,N'-dimethylacetamidinato)tin(IV) is prepared using
tin(IV) chloride, SnCl.sub.4;
tetrakis(N,N'-dimethylacetamidinato)tellurium(IV) is prepared from
TeCl.sub.4; and tetrakis(N,N'-dimethylacetamidinato)uranium(IV) is
prepared in using uranium(IV) chloride, UCl.sub.4.
Example 15
Atomic layer deposition of hafnium oxide from
tetrakis(N,N'-dimethylbutyramidinato)hafnium(IV) and ozone
10 mmol cm.sup.-2 doses of the vapor of
tetrakis(N,N'-dimethylpropionamidinato)hafnium(IV) from a direct
liquid injection system at 200.degree. C. are introduced with an
exposure of 10 Torr-sec in to an ALD reactor at 400.degree. C.,
alternately with 20 nmol cm.sup.-2 doses of ozone at an exposure of
10 Torr-sec. A film of hafnium oxide is deposited conformally
inside narrow holes with high aspect ratio of 80:1.
Example 16
Atomic Layer Deposition of hafnium oxide from
tetrakis(N,N'-dimethylbutyramidinato)hafnium(IV) and water
vapor
10 nmol cm.sup.-2 doses of the vapor of
tetrakis(N,N'-dimethylpropionamidinato)hafnium(IV) from a direct
liquid injection system at 200.degree. C. are introduced with an
exposure of 10 Torr-sec in to an ALD reactor at 400.degree. C.,
alternately with 20 nmol cm.sup.-2 doses of water vapor at an
exposure of 10 Torr-sec. A film of hafnium oxide is deposited
conformally inside narrow holes with high aspect ratio of 80:1.
Example 17
Atomic layer deposition of hafnium nitride from
tetrakis(N,N'-dimethylbutyramidinato)hafnium(IV) and ammonia
10 nmol cm.sup.-2 doses of the vapor of
tetrakis(N,N'-dimethylpropionamidinato)hafnium(IV) from a direct
liquid injection system at 200.degree. C. are introduced with an
exposure of 10 Torr-sec in to an ALD reactor at 400.degree. C.,
alternately with 20 nmol cm.sup.-2 doses of ammonia at an exposure
of 10 Torr-sec. A film of hafnium nitride is deposited conformally
inside narrow holes with high aspect ratio of 80:1.
Other variations on the synthetic methods and other metal(IV)
amidinate compounds will be apparent to those of skill in the
art.
* * * * *